CN110170255A - A kind of preparation method based on the super hydrophilic film of polyacrylonitrile - Google Patents
A kind of preparation method based on the super hydrophilic film of polyacrylonitrile Download PDFInfo
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- CN110170255A CN110170255A CN201910474129.9A CN201910474129A CN110170255A CN 110170255 A CN110170255 A CN 110170255A CN 201910474129 A CN201910474129 A CN 201910474129A CN 110170255 A CN110170255 A CN 110170255A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
- B01D71/42—Polymers of nitriles, e.g. polyacrylonitrile
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
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Abstract
The present invention designs a kind of preparation method based on the super hydrophilic film of polyacrylonitrile, it is characterized in that the preparation method of super hydrophilic film is prepared according to the following steps: one, prepare the super hydrophilic film of polyacrylonitrile: the polyacrylonitrile and active additive of content certain first are configured to polymer solution, and coating film forming is placed on inversion of phases in alkaline solution and prepares the super hydrophilic film of polyacrylonitrile；Two, prepare certain density hydrochloric acid solution, three, by film obtained in step 1 after deionized water is rinsed, immerse the hydrochloric acid solution certain time that step 2 obtains, post-processing obtains super hydrophilic seperation film.Operation of the present invention is simple, and a step realizes constructing for ultra-hydrophilic surface, and prepared super hydrophilic polyacrylonitrile film hydrophily is excellent, contact angle < 3o, the complete wetting in 0.5s, and surface hydrophilic structure will not change, and have " permanent " water-wet behavior.This method is suitable for preparing super hydrophilic polyacrylonitrile-radical ultrafiltration membrane and super hydrophilic polyacrylonitrile-radical microfiltration membranes, has broad prospect of application.
Description
Technical field
The present invention relates to a kind of preparation methods of film.
Background technique
Hydrophilic material as new material increasingly by the concern of people, since its surface has excellent hydrophily,
It is used widely in fields such as the depollution of environment, outdoor protection, health care, agricultural production, food packagings.Especially surface parent
Aqueous thin-film material is even more to obtain the favor of numerous researchers.
Surface wettability is one of important feature of the surface of solids, is usually come with contact angle (Contact angle, CA)
Characterize the infiltration degree of liquid versus solid.It is super hydrophilic generally refer to water droplet can complete drawout on the surface of the material, make contact angle
Equal or close in 0 °.It is answered extensively currently, ultra-hydrophilic surface obtains in the fields such as self-cleaning, antifog, antifouling, water-oil separating
With, and hot transmitting, microfluidic control, biomolecule fixation, accumulation rainwater, in terms of also show potential application before
Scape.
However, in actual application, existing method is related to the technique stream of expensive instrument and equipment or complexity more
Journey, it is difficult to realize the preparation of large area ultra-hydrophilic surface, and the influence vulnerable to external conditions such as light, heat, oxygen, not be able to satisfy length
The requirement that phase uses.In addition to this, the persistence of ultra-hydrophilic surface is also to restrict a key factor of its application, due to super close
Water surface has high surface energy, is easy to be converted to low-surface-energy direction to reach stable state, will lead to it and lose super parent
Aqueous energy, therefore the preparation method for developing a kind of simple and easy super hydrophilic film has very big market prospects and application value.
Summary of the invention
The object of the present invention is to provide a kind of simple preparation methods of super hydrophilic film, realize the purpose for constructing water-wetted surface.
A kind of preparation method based on the super hydrophilic film of polyacrylonitrile, specifically prepares according to the following steps:
One, prepare the super hydrophilic film of polyacrylonitrile: dissolving a polymer in solvent first, configuration containing 1% polyethers ammonia of mass fraction,
The epoxy-capped polyethylene glycol of mass fraction 1%, the silane coupling agent KH560 that mass fraction is 2%, mass fraction are 8% polypropylene
The N-Methyl pyrrolidone mixed with polymers solution that nitrile and mass fraction are 88%, and formed a film using the solution coating.By this kind
Film is placed in the NaOH coagulating bath of mass fraction 8%, and 50oUnder C, inversion of phases 3h, it is super hydrophilic that a step phase inversion prepares polyacrylonitrile
Film；
Two, prepare hydrochloric acid solution: compound concentration is 0.5 molL-1Hydrochloric acid solution；
Three, the super hydrophilic film of step 1 preparation is immersed in the hydrochloric acid solution that step 2 obtains after deionized water is rinsed, is impregnated
It is taken out after 2h, after being placed in distilled water overnight, obtains super hydrophilic seperation film through alcohol treatment.
It further limits, is respectively 5% ~ 18% in polyacrylonitrile mass fraction described in step 1.
It further limits, in polyetheramine described in step 1, epoxy terminated polyethylene glycol and silane coupling agent KH560
Mass fraction is respectively 0.1% ~ 3%, 0.2% ~ 6%, 0 ~ 1.0%.
It further limits, it is 5% ~ 12% that alkali, which induces the mass fraction of NaOH in a step phase inversion, in step 1.
It further limits, it is 20 ~ 50 DEG C that alkali described in step 1, which induces alkali coagulation bath temperature in a step phase inversion,.
It further limits, a length of 2 ~ 20h when alkali coagulating bath in one step phase inversion of alkali induction described in step 1.
The invention has the advantages that the one, present invention has highly hydrophilic polyacrylonitrile film using step phase inversion preparation.Behaviour
Make simple, the inversion of phases process i.e. super hydrophilic modification of realization film, the application prospect with large-scale production；Two, the present invention uses
Polyethylene glycol (peg) molecule with reactivity is as additive, and under aqueous slkali effect, reactive polyethylene glycol molecule can be sent out
Raw cross-linking reaction forms the hydrophilic molecule that main chain contains ether oxygen structure, forms new molecule and twines with polyacrylonitrile generation physics
Knot, is fixed on film surface, to assign film more excellent hydrophilicity；Three, super hydrophilic film prepared by the present invention has multilayer
The semi-interpenetrating network polymer of secondary hydrophilic-structure, the feature are containing the interpenetrating networks that can play the role of " forcing compatible ", no
It intertwine with each other to form an entirety with polymer molecule, cannot free, so that the hydrophilic film be made to have excellent stability, obtain
Durable hydrophilic effect.Prepared super hydrophilic polyacrylonitrile film hydrophily is excellent through the invention, contact angle < 3o, and can realize
Complete wetting in 0.5s.It is more excellent that polyacrylonitrile film hydrophily prepared by addition PEG is blended compared to tradition, and surface is close
Water-bound will not change, and have " permanent " water-wet behavior.
Using following verification experimental verifications effect of the present invention:
Test one: a kind of preparation method based on the super hydrophilic film of polyacrylonitrile is specifically prepared according to the following steps:
One, prepare the super hydrophilic film of polyacrylonitrile: dissolving a polymer in solvent first, configuration containing 1% polyethers ammonia of mass fraction,
The epoxy-capped polyethylene glycol of mass fraction 1%, the silane coupling agent KH560 that mass fraction is 2%, mass fraction are 8% polypropylene
The N-Methyl pyrrolidone mixed with polymers solution that nitrile and mass fraction are 88%, and formed a film using the solution coating.By this kind
Film is placed in the NaOH coagulating bath of mass fraction 8%, and 50oUnder C, inversion of phases 3h, it is super hydrophilic that a step phase inversion prepares polyacrylonitrile
Film；
Two, prepare hydrochloric acid solution: compound concentration is 0.5 molL-1Hydrochloric acid solution；
Three, the super hydrophilic film of step 1 preparation is immersed in the hydrochloric acid solution that step 2 obtains after deionized water is rinsed, is impregnated
It is taken out after 2h, after being placed in distilled water overnight, obtains super hydrophilic seperation film through alcohol treatment.
The super hydrophilic polyacrylonitrile film of this test preparation, contact angle 2.5 are detected using contact angle testero, in 0.3 s
Complete wetting can be achieved, after impregnating protein solution for 24 hours, after simple cleaning, contact angle 4o, still it is able to maintain super hydrophilicity.
Test two: a kind of preparation method of super hydrophilic film is specifically prepared according to the following steps:
One, it prepares the super hydrophilic film of polyacrylonitrile: dissolving a polymer in solvent first, configuration contains 1.5 % polyethers of mass fraction
The epoxy-capped polyethylene glycol of ammonia, mass fraction 3%, the diformazan that mass fraction is 8% polyacrylonitrile and mass fraction is 87.5%
Base formamide mixed with polymers solution, and formed a film using the solution coating.This kind of film is placed in the NaOH solidification of mass fraction 8%
In bath, 50oUnder C, inversion of phases 2h, a step phase inversion prepares the super hydrophilic film of polyacrylonitrile；
Two, prepare hydrochloric acid solution: compound concentration is 0.2 molL-1Hydrochloric acid solution；
Three, the super hydrophilic film of step 1 preparation is immersed in the hydrochloric acid solution that step 2 obtains after deionized water is rinsed, is impregnated
It is taken out after 2h, after being placed in distilled water overnight, obtains super hydrophilic seperation film through alcohol treatment.
The super hydrophilic polyacrylonitrile film of this test preparation, contact angle 3.5 are detected using contact angle testero, in 0.4 s
Complete wetting can be achieved, after impregnating protein solution 48h, after simple cleaning, contact angle 6.4o, still it is able to maintain Superhydrophilic
Energy.
Test three: one prepares the super hydrophilic film of polyacrylonitrile: dissolving a polymer in solvent first, configuration contains quality point
The epoxy-capped polyethylene glycol of several 2% polyethers ammonia, mass fraction 3%, the silane coupling agent KH560 that mass fraction is 2%, quality point
Number is the N-Methyl pyrrolidone mixed with polymers solution that 8% polyacrylonitrile and mass fraction are 85%, and is applied using the solution
Cloth film forming.This kind of film is placed in the NaOH coagulating bath of mass fraction 8%, 50oUnder C, inversion of phases 3h, step phase inversion preparation
The super hydrophilic film of polyacrylonitrile；
Two, prepare hydrochloric acid solution: compound concentration is 0.4 molL-1Hydrochloric acid solution；
Three, the super hydrophilic film of step 1 preparation is immersed in the hydrochloric acid solution that step 2 obtains after deionized water is rinsed, is impregnated
It is taken out after 2h, after being placed in distilled water overnight, obtains super hydrophilic seperation film through alcohol treatment.
The super hydrophilic polyacrylonitrile film of this test preparation, contact angle 1.5 are detected using contact angle testero, in 0.1 s
Complete wetting can be achieved, after impregnating protein solution 96h, after simple cleaning, contact angle < 3o, it is still able to maintain super hydrophilicity, is soaked
Bubble remains to be kept in contact angle < 7 after one montho。
A kind of preparation method based on the super hydrophilic film of polyacrylonitrile, it is characterised in that the preparation method of super hydrophilic film be by with
Lower step preparation: one, preparing the super hydrophilic film of polyacrylonitrile: dissolving a polymer in solvent first, configuration contains mass fraction
The epoxy-capped polyglycol solution of 1% polyethers ammonia, mass fraction 1%, the silane coupling agent KH560 that mass fraction is 2%, quality
The N-Methyl pyrrolidone mixed with polymers solution that score is 8% polyacrylonitrile and mass fraction is 88%, and utilize the solution
Coating film forming.This kind of film is placed in the NaOH coagulating bath of mass fraction 8%, 50oUnder C, inversion of phases 3h, a step inversion of phases legal system
The standby super hydrophilic film of polyacrylonitrile；Two, prepare hydrochloric acid solution: compound concentration is 0.5 molL-1Hydrochloric acid solution；Three, by step
The super hydrophilic film of one preparation immerses in the hydrochloric acid solution that step 2 obtains after deionized water is rinsed, and takes out, is placed on after impregnating 2h
After staying overnight in distilled water, super hydrophilic seperation film is obtained through alcohol treatment.Operation of the present invention is simple, and a step realizes ultra-hydrophilic surface
It constructs, prepared super hydrophilic polyacrylonitrile film hydrophily is excellent, it can be achieved that contact angle < 3 through the inventiono, and can realize
Complete wetting in 0.5s.It is more excellent that polyacrylonitrile film hydrophily prepared by addition PEG is blended compared to tradition, and surface is close
Water-bound will not change, and have " permanent " water-wet behavior.This method is suitable for preparing super hydrophilic polyacrylonitrile-radical ultrafiltration membrane
With super hydrophilic polyacrylonitrile-radical microfiltration membranes, there is broad prospect of application.
Claims (6)
1. one, preparing the super hydrophilic film of polyacrylonitrile: dissolving a polymer in solvent first, configuration contains 1% polyethers of mass fraction
The epoxy-capped polyethylene glycol of ammonia, mass fraction 1%, the silane coupling agent KH560 that mass fraction is 2%, mass fraction are 8% poly-
The N-Methyl pyrrolidone mixed with polymers solution that acrylonitrile and mass fraction are 88%, and formed a film using the solution coating, it will
This kind of film is placed in the NaOH coagulating bath of mass fraction 8%, and 50oUnder C, inversion of phases 3h, it is super that a step phase inversion prepares polyacrylonitrile
Hydrophilic film；
Two, prepare hydrochloric acid solution: compound concentration is 0.5 molL-1Hydrochloric acid solution；
Three, the super hydrophilic film of step 1 preparation is immersed in the hydrochloric acid solution that step 2 obtains after deionized water is rinsed, is impregnated
It is taken out after 2h, after being placed in distilled water overnight, obtains super hydrophilic seperation film through alcohol treatment.
2. a kind of preparation method of super hydrophilic film according to claim 1, it is characterised in that described in step 1 poly- third
Alkene nitrile mass fraction is respectively 5% ~ 18%.
3. a kind of preparation method of super hydrophilic film according to claim 1, it is characterised in that polyethers described in step 1
Amine, epoxy terminated polyethylene glycol and KH560 mass fraction are respectively 0.1% ~ 3%, 0.2% ~ 6%, 0 ~ 1.0%.
4. a kind of preparation method of super hydrophilic film according to claim 1, it is characterised in that alkali induces a step in step 1
The mass fraction of NaOH is 5% ~ 12% in phase inversion.
5. a kind of preparation method of super hydrophilic film according to claim 1, it is characterised in that alkali described in step 1 lures
Leading alkali coagulation bath temperature in a step phase inversion is 20 ~ 50 DEG C.
6. a kind of preparation method of super hydrophilic film according to claim 1, it is characterised in that alkali described in step 1 lures
Lead a length of 2 ~ 20h when alkali coagulating bath in a step phase inversion.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111298660A (en) * | 2020-02-27 | 2020-06-19 | 浙江理工大学 | Preparation method of anti-fouling composite nanofiltration membrane with strong stability |
| CN111672328A (en) * | 2020-06-04 | 2020-09-18 | 中国科学技术大学 | Carboxylated polyacrylonitrile porous membrane for removing fluorine and preparation method thereof |
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| WO2001097957A1 (en) * | 2000-06-23 | 2001-12-27 | Lg Chemical Co. Ltd. | Multi-component composite membrane and method for preparing the same |
| CN1973972A (en) * | 2006-12-01 | 2007-06-06 | 北京工业大学 | Prepn process of reinforced hybrid organic-inorganic film |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111298660B (en) * | 2020-02-27 | 2021-12-07 | 浙江理工大学 | Preparation method of anti-fouling composite nanofiltration membrane with strong stability |
| CN111672328A (en) * | 2020-06-04 | 2020-09-18 | 中国科学技术大学 | Carboxylated polyacrylonitrile porous membrane for removing fluorine and preparation method thereof |
| CN111672328B (en) * | 2020-06-04 | 2021-10-22 | 中国科学技术大学 | Carboxylated polyacrylonitrile porous membrane for removing fluorine and preparation method thereof |
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